Construction of Shallow Surface States through Light Ni Doping for High‐Efficiency Photocatalytic Hydrogen Production of CdS Nanocrystals

Ni‐doped CdS nanowires were synthesized by a simple one‐step method. X‐ray diffraction, X‐ray photoelectron spectroscopy, and photoluminescence spectroscopy confirmed that light Ni doping can form shallow surface states due to the presence of substitutional Ni ions, and heavy Ni doping can form deep surface states due to the presence of interstitial Ni ions. Surface photovoltage spectroscopy and transient photovoltage measurements revealed that the shallow surface states can prolong the lifetime of the photogenerated charge carriers, whereas the deep surface states lead to recombination of the photogenerated charge carriers. The relationship between different surface states and the photocatalytic performance of CdS nanocrystals are discussed. The enhanced density of shallow surface states due to light Ni doping significantly promotes photocatalytic H₂ production.     

SrTiO3/TiO2 Hybridstructure as Photoanode in Dye‐Sensitized Solar Cell

In dye‐sensitized solar cells (DSSCs), the charge recombination at the TiO₂/dye/electrolyte interface greatly influences the photoelectron conversion efficiency. Hybrid semiconductor materials with matched band potentials are designed to reduce the charge recombination. In this study, SrTiO₃/TiO₂ hybridstructure was synthesized by using TiO₂ nanoparticles as template in a hydrothermal, showing a negative shift in the flat band potential. The DSSC with the SrTiO₃/TiO₂ anode exhibits an increased photovoltage and a reduced photocurrent. The suppression of charge recombination at the TiO₂/dye/electrolyte interface was observed in the electrochemical impedance spectroscopy, causing an improvement in the photovoltage. However, the SrTiO₃/TiO₂ system shows an obstructed electrons injection from the dye to SrTiO₃/TiO₂, limiting the photocurrent performance. The photoelectrochemical properties of the SrTiO₃/TiO₂ system are discussed in detail herein.     

N, S共掺杂纳米TiO2：水解-溶剂热法合成及可见光催化活性

采用简单的两相分离的水解-溶剂热法,以硫脲为非金属原料,可控地制备了N,S共掺杂的纳米TiO₂。所获得的纳米TiO₂平均粒径为10nm、粒径分布集中,且分散性好。N,S共掺杂拓展了纳米TiO₂对可见光的响应范围。气氛可控的表面光电压谱（SPS）的测试结果表明,N,S共掺杂引起的表面态能够捕获光生空穴,进而有利于光生电荷分离。在可见光催化氧化水产氧及降解污染物乙醛的过程中,共掺杂的纳米TiO₂表现出了高的活性,甚至优越于N掺杂的。这主要归因于N,S共掺杂的纳米TiO₂分散性好、可见光吸收强和光生电荷分离高。     

N,S共掺杂纳米TiO_2:水解-溶剂热法合成及可见光催化活性

采用简单的两相分离的水解-溶剂热法,以硫脲为非金属原料,可控地制备了N,S共掺杂的纳米TiO2。所获得的纳米TiO2平均粒径为10 nm、粒径分布集中,且分散性好。N,S共掺杂拓展了纳米TiO2对可见光的响应范围。气氛可控的表面光电压谱(SPS)的测试结果表明,N,S共掺杂引起的表面态能够捕获光生空穴,进而有利于光生电荷分离。在可见光催化氧化水产氧及降解污染物乙醛的过程中,共掺杂的纳米TiO2表现出了高的活性,甚至优越于N掺杂的。这主要归因于N,S共掺杂的纳米TiO2分散性好、可见光吸收强和光生电荷分离高。     

Soft Lattice and Defect Covalency Rationalize Tolerance of β‐CsPbI3 Perovskite Solar Cells to Native Defects

Although all‐inorganic metal halide perovskites (MHPs) have shown tremendous improvement, they are still inferior to the hybrid organic–inorganic MHPs in efficiency. Recently, a conceptually new β‐CsPbI₃ perovskite reached 18.4 % efficiency combined with good thermodynamic stability at ambient conditions. We use ab initio non‐adiabatic molecular dynamics to show that native point defects in β‐CsPbI₃ are generally benign for nonradiative charge recombination, regardless of whether they introduce shallow or deep trap states. These results indicate that MHPs do not follow the simple models used to explain defect‐mediated charge recombination in the conventional semiconductors. The strong tolerance is due to the softness of the perovskite lattice, which permits separation of electrons and holes upon defect formation, and only allows carriers to couple to the low‐frequency vibrations. Both factors decrease notably the non‐adiabatic coupling and slow down the dissipation of energy to heat.     

The effects of pyridine derivative additives on interface processes at nanocrystalline TiO2 thin film in dye‐sensitized solar cells

2‐Methyl‐4‐propoxypyridine, a new pyridine derivative, has been synthesized and used as an additive in the liquid electrolyte of dye‐sensitized solar cells (DSSCs). Compared with 2‐methylpyridne and 4‐tert‐pyridine, they were employed to study the influence of the pyridine derivative additives on the rate of recombination at the electrode/dye/electrolyte interfaces and band edge shift of TiO₂, which were measured by time‐resolved mid‐infrared absorption spectroscopy and Mott–Schottky analysis, respectively. It was found that the rate of interfacial charge recombination was enhanced when the pyridine derivative additives were present in the electrolyte. Meanwhile, the additives caused a negative shift of the band edge. However, the net effect of pyridine derivative addition was to improve the open‐circuit photovoltage according to the photoelectrochemical measurement, indicating that negative shift of conduction band of TiO₂ was a predominant factor in improving the open‐circuit photovoltage. Also, the result was strongly supported by the dark current measurement. Therefore, it provides a microscopic account for the function of the pyridine derivative additives on the open‐circuit photovoltage enhancement of the DSSCs. Furthermore, the decrease of the short‐circuit photocurrent of the cells was also attributed to the slower dye regeneration due to the addition of additives from the results of cyclic voltammetry measurement. Copyright © 2007 John Wiley & Sons, Ltd.     

Chemical synthesis of Ni/TiO<Subscript>2</Subscript> nanophotocatalyst for UV/visible light assisted degradation of organic dye in aqueous solution

The Ni/TiO₂ nanoparticles with different Ni dopant content were prepared by a modified sol–gel method. The structure and photoinduced charge properties of the as-prepared catalysts were determined using X-ray diffraction, transmission electron microscopy, UV–vis diffuse reflectance spectroscopy and surface photovoltage spectroscopy techniques, and the photocatalytic efficiency of these catalysts was tested using an organic dye. It was shown that Ni modification could greatly enhance the photocatalytic efficiency of these nanocomposite catalysts by taking the photodegradation of methyl orange as a model reaction. With appropriate ratio of Ni and TiO₂, Ni/TiO₂ nanocomposites showed the superior photocatalytic activity than the single TiO₂ nanoparticles. Surface photovoltage spectra demonstrated that Ni modification could effectively inhibit the recombination of the photoinduced electron and holes of TiO₂. This electron–hole pair separation conditions are responsible for the higher photocatalytic performance of Ni/TiO₂ nanocomposites in the visible region of electromagnetic spectrum.     

Enhancing the Performance of Dye‐Sensitized Solar Cells with a Gold‐Nanoflowers Box

To improve the electron collection, electron lifetime, and light‐harvesting efficiency of dye‐sensitized solar cells simultaneously, Au nanoflowers were prepared and used to cover the entire TiO₂ film. Deposition of Au nanoflowers around the TiO₂ film formed a light‐scattering “box” that covered the entire TiO₂ film. Compared with a light‐scattering layer that only covers the top surface of TiO₂, the Au‐nanoflowers box exhibited better light‐harvesting efficiency due to omnidirectional light scattering, faster electron transport (attributed to the formation of electron channels between the metallic Au nanoflowers and the electron‐collection electrode), and slower charge recombination. As a consequence, the short‐circuit photocurrent and open‐circuit photovoltage were both enhanced significantly, which improved the power conversion efficiency from 8.12 to 10.91 % (34 %) when an Au‐nanoflowers box was wrapped around the photoanode.     

Preparation of Cu-doped TiO2 via refluxing of alkoxide solution and its photocatalytic properties

Cu-doped TiO₂ was prepared by the refluxing of a mixture of copper and titanium alkoxides. The refluxing improved the Cu²⁺ dispersion in the TiO₂ and formed effective Ti–O–Cu bonds. The impurity states due to the highly dispersed Cu²⁺ were presumed to trap the electrons in the conduction band of the TiO₂ and prevent charge recombination of the electrons and holes. Consequently, the prolonged charge separation duration was suggested to enhance the photocatalytic activity of the Cu-doped TiO₂. This enhancement was confirmed by the hydroxyl radical generation and organic compound degradation. The Ti–O–Cu bonds and electronic interaction between Cu and Ti should effectively promote the electron trapping. The Cu-doped TiO₂ exhibited a visible light-induced activity due to the transition from the TiO₂ valence band to the Cu²⁺ impurity states.     

Correlating Photovoltaic Performance of Dye-Sensitized Solar Cell to the Film Thickness of Titania via Numerical Drift-Diffusion Simulations

The thickness of TiO₂ film is vital to realize the optimization on photovoltaic performance of dye sensitized solar cells (DSSCs). Herein, the process of charge separation in DSSCs was simulated by using a drift-diffusion model. This model allows multiple-trapping diffusion of photo-generated electrons, as well as the back reaction with the electron acceptors in electrolyte, to be mimicked in both steady and non-steady states. Numerical results on current-voltage characteristics allow power conversion efficiency to be maximized by varying the thickness of TiO₂ film. Charge collection efficiency is shown to decrease with film thickness, whereas the flux of electron injection benefits from the film thickening. The output of photocurrent is actually impacted by the two factors. Furthermore, recombination rate constant is found to affect the optimized film thickness remarkably. Thicker TiO₂ film is suitable to the DSSCs in which back reaction is suppressed sufficiently. On the contrary, the DSSCs with the redox couple showing fast electron interception require thinner film to alleviate the charge loss via recombination. At open circuit, electron density is found to decrease with film thickness, which engenders not only the reduction of photovoltage but also the increase of electron lifetime.     

Surface photovoltage phase spectroscopy study of the photo-induced charge carrier properties of TiO2 nanotube arrays

By using the surface photovoltage(SPV) technique based on a lock-in amplifier,surface states located 3.1 eV below the conduction band of TiO 2 have been detected in TiO 2 nanotube arrays prepared by anodization of titanium foil in fluoride-based ethylene glycol solution.The photo-induced charge transportation behavior of TiO 2 nanotube arrays was also studied by qualitatively analyzing their SPV phase spectra measured under different external bias.When a negative bias was applied,carriers excited from surface states have the same transportation properties as those excited from the valence band;in contrast,when a positive bias was applied,these two kinds of photo-excited carriers exhibit different transportation behavior.     

Photosensitization of TiO2 nanoparticulate thin film electrodes by CdS nanoparticles

Surface photovoltage spectra (SPS) measurements of TiO₂ show that a large surface state density is present on the TiO₂ nanoparticles and these surface states can be efficiently decreased by sensitization using CdS nanoparticles as well as by suitable heat treatment. The photoelectrochemical behavior of the bare TiO₂ thin film indicates that the mechanism of photoelectron transport is controlled by the trapping/detrapping properties of surface states within the thin films. The slow photocurrent response upon the illumination can be explained by the trap saturation effect. For a TiO₂ nanoparticulate thin film sensitized using CdS nanoparticles, the slow photocurrent response disappears and the steady-state photocurrent increases drastically, which suggests that photosensitization can decrease the effect of surface states on photocurrent response. Electronic Publication     

Disinfection of Escherichia Coli Gram Negative Bacteria Using Surface Modified TiO2: Optimization of Ag Metallization and Depiction of Charge Transfer Mechanism

The antibacterial activity of silver deposited TiO₂ (Ag‐TiO₂) against Gram negative Escherichia coli bacteria was investigated by varying the Ag metal content from 0.10 to 0.50% on the surface of TiO₂. Ag depositions by the photoreduction method were found to be stable. Surface silver metallization was confirmed by EDAX and XPS studies. Photoluminescence studies show that the charge carrier recombination is less for 0.1% Ag‐TiO₂ and this catalyst shows superior bactericidal activity under solar light irradiation compared to Sol gel TiO₂ (SG‐TiO₂) due to the surface plasmon effect. The energy levels of deposited Ag are dependent on the Ag content and it varies from ?4.64 eV to ?1.30 eV with respect to the vacuum energy level based on atomic silver to bulk silver deposits. The ability of electron transfer from Ag deposit to O₂ depends on the position of the energy levels. The 0.25% and 0.50% Ag depositions showed detrimental effect on bactericidal activity due to the mismatch of energy levels. The effect of the EROS (External generation of the Reactive Oxygen Species by 0.1% Ag‐TiO₂) and IROS (Interior generation of Reactive Oxygen Species within the bacteria) on the bactericidal inactivation is discussed in detail.     

纳米TiO2的光生电荷迁移特性研究

利用场诱导光电压谱(简称FISPS)和瞬态光伏(简称TPV)技术研究了TiO₂的光生电荷的产生和传输机制.发现光生电荷在体块TiO₂上的迁移机制不同于在纳米TiO₂上的迁移机制，也不同于在结界面空间电荷区的迁移机制. 400 ℃处理的TiO₂颗粒表面具有大量的表面态，光生电荷被表面态捕获-释放机制控制着光伏行为的过程是慢过程. 800 ℃处理的TiO₂已经形成了完整的能带结构，光伏响应除了表现带-带跃迁外,还有一个在带边的自由激子带，光生电荷被表面自建场驱动进行传递的过程是快过程. 600 ℃处理的TiO₂混晶由锐钛矿型和金红石型两种构型组成，在两相之间存在着较低势垒的结界面．它的光伏响应受控于两种机制 ：光生电荷在两相间结界面空间电荷区的传输和在表面自建场驱动下的传输.当激发光强较小时，界面空间电荷区的光生电子由于积累的浓度较小而不能隧穿过结界面，这种场助隧穿只有在外场作用下才能发生.     

A comparative study on photoelectrochemical performance of TiO2 photoanodes enhanced by different polyoxometalates

Based on the incorporation of polyoxometalates (POMs) into TiO₂ film, the photoelectrochemical performance of POMs/TiO₂ anode was elucidated by comparative investigation on the electron transport and electron–hole recombination in POMs/TiO₂ anode. The photoelectrochemical performance of the POMs/TiO₂ anode was clearly dependent on the type and content of POMs. Compared to the TiO₂ anode, the POMs/TiO₂ anode with low POMs loadings (0.75%) displayed the enhanced photoelectrochemical performance, while the excessive content (7.5%) of POMs could almost cause a negative effect. Thus, POMs could act as either “shallow electron trap” or “deep electron trap” depending on the different types and contents of POMs. This study reveals that the introduction of POMs into TiO₂ anode could facilitate photogenerated electron transfer and reduce electron–hole recombination, which is urgently desired to develop advanced composite materials of POMs/TiO₂ for application in photoelectrochemical catalysis and solar cells.     

Understanding the Roles of Oxygen Vacancies in Hematite‐Based Photoelectrochemical Processes

Oxygen vacancy (V_O) engineering is an effective method to tune the photoelectrochemical (PEC) performance, but the influence of V_O on photoelectrodes is not well understood. Using hematite as a prototype, we herein report that V_O functions in a more complicated way in PEC process than previously reported. Through a comprehensive analysis of the key charge transfer and surface reaction steps in PEC processes on a hematite photoanode, we clarify that V_O can facilitate surface electrocatalytic processes while leading to severe interfacial recombination at the semiconductor/electrolyte (S‐E) interface, in addition to the well‐reported improvements in bulk conductivity. The improved bulk conductivity and surface catalysis are beneficial for bulk charge transfer and surface charge consumption while interfacial charge transfer deteriorates because of recombination through V_O‐induced trap states at the S‐E interface.     

介孔掺镧纳米晶TiO_2瞬态光伏与表面光声特性

结合瞬态光伏与表面光声技术,研究介孔掺镧nano-TiO2光生载流子分离与复合过程及其能量转换机制.结果表明:锐钛矿中两种不同光伏特性的缺陷态具有光生载流子扩散距离短,复合速度快的特点;镧掺杂增加体缺陷态对于光伏效应的贡献,但在某种程度上抑制主带隙的电荷分离;模板剂种类对于主带隙电子-空穴对的分离与复合过程,以及亚带隙无辐射跃迁引起的晶格振动均有显著的影响.结果证实了样品表面光声与瞬态光伏现象之间存在明显的能量互补关系.     

Photovoltaic Properties of Titanium Dioxide Nanowires with Different Crystal Structures

Titanium dioxide(TiO₂) nanowires with different crystal structures were successfully synthesized, and their charge transfer properties were further investigated by surface photovoltage(SPV), transient photovoltage(TPV) and surface photocurrent(SPC) techniques. The results reveal that both the surface states and the charge transfer rate of different TiO₂ nanowires are highly dependent on their crystal structures.     

CdS/TiO2–SrTiO3 heterostructure nanotube arrays for improved solar energy conversion efficiency

TiO₂–SrTiO₃ heterostructure nanotube arrays have been utilized as a novel oxide substrate for CdS quantum dot sensitized solar cells (QDSCs). SrTiO₃ on TiO₂ surface passivates surface states of TiO₂ and builds cascade-structured band alignment, which significantly reduces charge recombination at electrode surface. CdS/TiO₂–SrTiO₃ electrode exhibits a superior photoelectrochemical performance than CdS/TiO₂ electrode with ～ 70% increase in external quantum efficiency. This study suggests that the suppression of charge recombination at electrode surface is critical to efficient solar energy conversion.     

不同浓度Sn4+离子掺杂TiO2的结构、性质和光催化活性

采用溶胶-凝胶法制备出纯TiO₂和不同浓度Sn⁴⁺离子掺杂的TiO₂光催化剂(TiO₂-Snx%, x%代表Sn⁴⁺离子掺杂的TiO₂样品中Sn⁴⁺离子摩尔分数). 利用X 射线衍射(XRD)、X 射线光电子能谱(XPS)和表面光电压谱(SPS)确定了TiO₂-Snx%催化剂的晶相结构和能带结构, 结果表明: 当Sn⁴⁺离子浓度较低时, Sn⁴⁺离子进入TiO₂晶格, 取代并占据Ti⁴⁺离子的位置, 形成取代式掺杂结构(Ti_1-xSn_xO₂), 其掺杂能级在导带下0.38 eV处; 当Sn⁴⁺离子浓度较高时, 掺入的Sn⁴⁺离子在TiO₂表面生成金红石SnO₂, 形成TiO₂和SnO₂复合结构(TiO₂/SnO₂), SnO₂的导带位于TiO₂导带下0.33 eV处. 利用瞬态光电压谱和荧光光谱研究了TiO₂-Snx%催化剂光生载流子的分离和复合的动力学过程, 结果表明, Sn⁴⁺离子掺杂能级和表面SnO₂能带存在促进光生载流子的分离, 有效地抑制了光生电子与空穴的复合; 然而, Sn⁴⁺离子掺杂能级能更有效地增加光生电子的分离寿命, 提高了光生载流子的分离效率, 从而揭示了TiO₂-Snx%催化剂的光催化机理.